Catalyzer and method of making same



T a M E n 5 ac o N as To R 65 o R 15 0e cs. OF HYOR 0G a N C. ELLIS ETAL CATALYZER AND METHOD OF MAKING SAME Filed July 15, 1920 Pzmou OFHwronoszunnou In "\NUTES Iuv: Rs: Qmgl $4 Patented Dec. 9, 1924.

UNITED STATES PATENT OFFICE.

GARLETON ELLIS, OF MON'IOLAIR, AN D HARRY M. WEBER, F BLOOMFIELD, NEWJEE- SEY; SAID WEBER ASSIGNOR OF HIS ENTIRE RIGHT TO ELLIS-FOSTERCOMPANY,

A CORPORATION OF NEW JERSEY.

CATALYZER AND METHOD OF MAKING SAME.

Application filed July 15,

To all whom it may concern:

Be it known that we, CARLETON ELLIS and HARRY M. WEBER, citizens of theUnited States, and residents, respectively, of Montclair, in the countyof Essex and State of New Jersey, and'Bloomfield, in the county of Essexand State of New Jersey, have invented certain new and usefulImprovements in ,Catalyzers and Methods of Making Same, of which thefollowing is a specitication.

This invention relates to a method of making catalyzers adapted for useas hydrogen carriers and particularly useful in the hydrogenation offatty oils and like purposes.

The invention involves the comminution of the catalytic raw material ina suitable medium preferably one of a liquid character or one whichbecomes liquid on exposure to heat; such oomminution being car ried outto an extent suflicient to yield catalytic material having the desiredcatalytic activity such as will be more fully herein- 5 after explained.

As a suitable source of catalytic material various compounds of nickelmay be employed. Of such compounds the basic compounds of nickel yieldsatisfactory results Nickel carbonate or the basic carbonate of nickel,nickel hydroxid and in some cases the oxide may be used. Correspondingcompounds of copper and cobalt similarly may be utilized. In some casesmixed catalyzers consisting of nickel and copper, co-

balt or other metal may be used. The employment of the rare metals suchas platinum, palladium, osmium and the like is not excluded althoughgenerally speaking not recommended for making a catalyzer of the type.described herein. The rare metals are quite expensive and satisfactoryresults are obtained from base metals such as those indicated. Inaddition to the foregoing organic salts of these metals such for exampleas nickel formate, acetate, benzoate and the like or mixtures orcombinations involving bothinorganic and organic radicals may beutilized such for example as nickel carbonate and formate. A

As a material or vehicle in which to carry out the comminutionpreferably there is employed a hydrocarbon such as a petro- 1920. SerialNo. 396,599.

leum oil of high boiling point and also Waxes, for example paraflin wax,petroleum jelly, petrolatuni free from sulphur compounds and the like.It is also possible to employ vegetable oils although in the finalreduction operation vegetable oils are usually not as desirable as thehigh temperatures necessary bring about more or less decomposition.Besides these oily, fatty or waxy materials other vehicles may beemployed such as volatile substances like ether or gasoline or mixturesof gasoline with the less volatile material kerosene. In some casesglycerine may be used or glycerine diluted with water. Good results havebeen obtained by grinding with water alone and subsequently evaporatingto dryness and carrying out reduction under suitable conditions. r

In carrying out the comminution various apparatus may be employed toenable the process to be carried through effectively. Preferably a ballmill or pebble mill is employed and when preparing the nickel catalyzersuch a ball mill may be lined with brick or porcelain or may be made ofnickel, when the presence of any other metal might prove objectionablein the product. Steel rolls also may be used for grinding and comforexample with volatile materials the temperature is preferably lower, orcooling of the mill may be resorted to in-some cases.

It is important tohave the proportion of oil or other vehicle such thatthe grinding may be carried out effectively. IVhen grinding nickelcarbonate for example a plastic mass maybe prepared which grinds readilyfor a time but as the carbonate becomes finer the mass stiffens andfinally clings to the sides of the ball mill and is not so easilyground. In fact in a small laboratory mill considerable difficulty hasbeen found with percentages of oil which originally made a good flowingmass of soft putty like material. In a general Way the proportion of oilto material may be varied to say one part of oil to two parts of thematerial up to six parts of oil to one part of material; but of coursesuch proportions depend in part at least on the character of theoriginal material which is being ground, some compounds have muchgreater absorptive capacities for oil than others.

In the present invention it is one object to prepare a catalyzerconcentrate as for example a mixture of nickel and for examplehydrocarbon vehicle co ntaining only enough of the latter to seal theparticles of nickel so that they will not oxidize and thus enable theshipment of the catalyzer in a concentrated form to long distanceswithout substantial deterioration. A hydrocarbon vehicle is quitesatisfactory for this purpose as it is comparatively inert. Thus forexample paraflin wax is a very satisfactory sealing medium and enablesthe product to be'pressed or molded into the form of cakes which areconvenient for handling and shipping. In like manner petroleum jellyserves to protect the nickel particles from oxidation but in this case amore plastic product is secured. However there is no value in havingexcessive amounts of wax, Vaseline or other vehicle present when anickel concentrate is desired as shipping of any excess quantities ofthe grinding and sealing medium is sometimes objectionable. Moreover toproperly grind the material it is usually necessary to have an excess ofthe medium and in order to secure a high degree of concentration in thefinal product the excess of hydrocarbon may be removed by distillationwhen sufficiently volatile for the purpose. Thus mixtures of petroleumjelly and gasoline may be used and the gasoline subsequently distilled.Or the petroleum jelly may be distilled at a high tem perature andthedistillation .is accelerated by agitating the mass during heating. Inmaking a permanent form of catalyzer for shipping purposes saponifiableoils are not as satisfactory because some part of the nickel may reactwith any free fatty acid forming nickel soap or a soap of whatever metalmay be present and this action may affect the quality of the catalyzer.In addition to keeping the amount of hydrocarbon vehicle down to aminimum from the above standpoint, it may also be mentioned that whenhydrogenating vegetable oils it is not desirable. to introduce more thana small per cent of unsaponifiable matter and the presence of any largeamount of hydrocarbon oil or wax would be objectionable in some cases.

The grinding may be carried out until the originally rather coarsematerial is so line or so flocculated through the vehicle as to be veryslowly settling and in one case for rials free or substantially freefrom cata lyzer poisons so that pains are taken to exclude hydrocarbonoils containing sulphur or raw material such as nickel hydrate whichcontains sulphur, arsenic or other bodies having a depressing action onthe catalytic process.

The grinding of the material such for example as nickel carbonate in avehicle as H above described has a very decided effect on the catalyticactivity, when for example nickel carbonate of ordinary commercial gradeis used. Grinding such nickel carbonate in a dry state without thepresence of 1.

a vehicle is not effective in yielding a catalyzer of the highest typeof efficiency at least under any conditions which would be practical inthe usual type of hydrogenation plant. Nickel carbonate which has passedthrough the finest bolting cloth, as for example, 200 mesh cloth doesnot give the efiiciency that the same material affords when ground inoil. It is a rather remarkable fact that grinding in this manner doesachieve the results observed but by refer- (1118 to the accompanyingsheet or diagram it will be seen that the efi'ect of grinding Isdistinctly noticeable.

Before considering the chart in detail, the method of makingobservations, whereby the curves here presented were obtained, will befirst noted.

A description of the apparatus used for determining the efficiency ofthe various catalysts tested is as follows: A small map-1e boardplatform was mounted on a jointed standard in such a. manner as to allowthe platform to be oscillated rapidly; The platform was held in ahorizontal position, when at rest, by means of 4 springs attached toeach corner of the platform. The lower leg of the jointed standard wasattached to a solid table and the lower end of the springs were alsoattached to the table. Mounted on the platform was a small electric hotplate used for maintaining the temperature of the. oil and catalystbeing tested, at the desired point namely between and C. A suitablereceptacle for holding the flask containing a definite quantity of oiland catalyst inposition, was placed on the hot plate the walls of whichwere heat insulated by means of asbestos board. At one edge of thewooden platform there was attached an iron llll) rod which served as ahandle for shaking the. apparatus and which was also used as a supportfor a clamp to hold the flask in an upright position when being shaken.The neck of the flask was closed by means of a three hole rubberstopper, one of these holes being used for the insertion of athermometer to determine the temperature of the oil and the other twoholes for the insertion of tubes for the inlet and outlet of hydrogenfrom the flask. The inlet tube extended to the bottom of the flask andwas attached to the hydrogen supply, the hydrogen supply.

being regulated by means of a needle valve. The outlet tube was attachedby means of rubber tubing to an aspirator bottle. 1nserted in the rubbertubing between the outlet tube and the aspirator bottle was a' glass T,the third leg of which served as an outlet for the waste hydrogen duringthe passage of the hydrogen into the oil during hydrogenation and alsoas an outlet for flushing the air f1 om the flask when the hydrogenationwas first started. During the determination of the time required toabsorb a definite volume of hydrogen the outlet is closed by means ofrubber tubing and a clamp. The outlet of the aspirator bottle wascomiected by means of rubber tubing to a burette which was graduated toc. c. and had a capacity of 100 c. c. The aspirator bottle was filledwith water with a layer of oil on top of the water to act as a, seal andprevent moisture from getting into the hydrogen sup-ply.

The operation of the above apparatus was as follows: The oil andcatalyst was first heated to a temperature of between 180- 190 C. andthe flask then clamped in position on the hotplate. Suflicient hydrogenwas then passed from the hydrogen supply to flush out the air which wasin the flask primarily, with the out-let tube from the T open. After theair had been entirely removed from the flask 100 c. c. of hydrogen wasallowed to flow into the asp-irator bottle, the outlet tube from the Tclosed and the liquid in the burette leveled with the liquid in theaspirator bottle. The flask was the-n rapidly shaken back and forth andthe time required to absorb the 100 c. c; of hydrogen in the-aspiratorbottle determined, maintaining the level of the liquid in the buretteand the aspirator bottle throughout the operation; the determinationbeing therefore made at atmospheric temperature and pressure.

The time required to absorb 100 c. c. of hydrogen while the oil wasbeing shaken was taken every 5 minutes. During these 5 minute intervalsa fairly rapid stream of hydrogen was allowed to pass through the oilwhich approximates commercial practice.

In order that a comparison of the efficiency of various catalysts mightbe made,

a standard quantity, 250 grams of prime summer yellow cottonseed oil anda standard quantity of catalytically active material based on its nickelcontent was used. .5 of 1% of the weight of the oil used or theequivalent of 1.25 grams of nickel being the quantity of catalyticmaterial used in all of the determinations of catalytic activity whichfollow. The weighed quantity of catalyzer is first added to thecottonseed oil and the mixture brought up to a. temperature of between180 and 190 0., this procedune being a common practice in the industry.The flask containing the cottonseed oil and catalyst was then placed inthe apparatus which is more fully described above, the air flushed fromthe flask with hydrogen, and the time of absorption of 100 c. c. ofhydrogen by the cottonseed oil in the presence of the catalyst beingtested was immediately determined and the time in seconds required forthe absorption noted as the zero point. I

A steady stream of hydrogen was then allowed to pass through the oil fora period of five minutes and the time required for the oil to absorb 100cc of hydrogen was again determined. The procedure of allowing a steadystream of hydrogen to pass through the oil for a period of live minutesand the determination of the time required to absorb 100 c. c. ofhydrogen at the expiration of each live minute interval was carried outfor a period of one hours time of hydrogenation and the results plotted.

In the accompanying chart the curw marked A was prepared from theperformance of the catalyst prepared from dry nickel carbonate which hadbeen ground in a pebble mill to pass 200 mesh bolting cloth and thenreduced in .paraflin to an active catalytic state at a temperature of350360 C. for a period of one hour. One hour is a somewhat longer periodof time than is required to reduce small quantities of nickel carbonateto a catalytically active state but in order to standardize thereduction of the raw material we reduced the nickel salt at the desiredtemperature for this period of time in all cases. 50 parts by weight ofdry nickel carbonate and 100 parts by weight of paraffin was used inthis case and after reduction a quantity of the reducedmaterial'equivalent to 1.25 grams of nickel was used for testing thecatalytic activity of the reduced material.

The results obtained from a catalyst prepared from one part by weight ofnickel carbonate which was ground in a pebble mill for a period of fourhours with 6 parts by weight of mineral oil'is noted on the chart ascurve B. The product obtained after the grinding operation was of theconsistency of a thin cream and a small quantity when rubbed between thefingers did not show any Ill] all

signs of grittiness. The apparent size of some of the particles ofnickel carbonate when examined under the microscope with a magnificationof 1750 diameters was about the size of a head of a pin but the majorityof the particles were smaller. The reduction of the finely dividednickel carbonate in the mineral oil vehicle was then carried out at atemperature of 350-360 C. for a period of one hour and the catalyticetliciency determined in the manner described above.

The initial efliciency of the nickel carbonate which was ground in oilis very much higher than that of the nickel carbonate which was grounddry. The nickel carbonate ground in oil attained its greatest efficiencyafter 12 to 13 minutes of hydrogenation; while the nickel carbonatewhich was ground dry only attained its maximum efliciency after minutestime of hydrogenation. The eflicieney of the nickel carbonate ground inoil decreased very slowly until at the end of one hours time ofhydrogenation thetime required to absorb 100 c. c. of hydrogen was but13 seconds while in the case of the nickel carbonate which was grounddry the time required to absorb 100 c. of hydrogen was 36 seconds. It isevi dent therefore that the efficiency of the nickel carbonate whenground in oil and then reduced is much greater than when nickelcarbonate is finely ground without the use of oil.

Nickel formate when ground dry in a pebble mill to pass 200 mesh boltingcloth and then reduced in paraffin at a temperature between 250260 C.has a somewhat higher efliciency than that of the particular sample ofnickel carbonate when treated in the same manner. The curve marked C onthe chart was prepared from the results obtained from the performance'of nickel formate when treated in this manner and tested in theapparatus described above.

Curve D represents the results obtained from a catalyst prepared bygrinding one part by weight of nickel formate in a pebble mill with 6parts by weight of mineral oil for a period of four hours and inreducing the resultant product at a temperature of 250-260 C. for aperiod of one hour. The general appearance of the nickel formate groundin the oil was similar to the appearance of the product obtained fromgrinding nickel carbonate in oil, the size of the ground particles andthe consistency of the product being approximately the same and therewas no evidence of grittiness when a small sample of the ground productwas rubbed between-the fingers. The efiiciency of the reduced catalystwas then determined and the results noted on the accompanying V chartand marked curve D.

The initial efliciency of the nickel formate which was ground in oil wasmaterially higher than that of the nickel formate which was ground dryand in both cases the catalysts had worked up to their maximumefficiency after 12 to 13 minutes of hydrogenae tion. The efficiency ofboth catalysts then gradually decreased until at the expiration ofminutes hydrogenation the nickel formate catalyst which had been grounddry require-d 18.8 seconds to absorb 100 c. c. of hydrogen while thenickel formate catalyst which had been ground in oil required but 13seconds time to absorb 100 c. c. of hydrogen.

The reduction of the catalytic raw material in the medium as aforesaidmay take place in various ways as for example in the case of nickelformate by simply heating the mass to say 2l0 C. whereby tecompositionoccurs and catalytic nickel is formed. Or a mixture of nickel and coppercarbonates which'have been ground in Vaseline may be heated to 250 orhigher and a current of hydrogen or other reducing gas passedtherethrough until reduction is effected.

Another method which is preferred because of its simplicity andcheapness is that of heating the hydrocarbon vehicle with its ground upcatalytic raw material to a temperature at which cracking takes placewhereby reduction occurs and .the catalytic concentrate is obtained.Under these conditions a distillation and consequent ren'ioval of moreor less of the vehicle results. A temperature of 340 to about 400 isusually satisfactory for making a catalyzer under the latter conditions.Agitation of the mass while being heated is useful. may contain variouspercentages of nickel from that required in ordinary catalyticoperations that is usually less than 1%, up to say 75% of nickel. Auseful form of concentrate is one containing 25 to 30% of nickel ornickel and cobalt material. while a more desirable one for shipping tolong distances contains (30 'to 70% of the catalytic material. Thenickel made by reduction in a vehicle is not strictly speaking of apyrophoric character and in fact by extraction of the hydrocarbon withbenzol or other solvent a metal powder may be obtained which may beexposed to the air for a considerable period without substantial loss.in catalytic power. However for shipping purposes as aforesaid it isdesirable to have av certain.

does not apply in most cases and very active catalyzer maintaining itspower ,over the hydrogenation per od n the desired manner The productmay be readily obtained without resorting to the extra step or expenseof grinding the reduced nickel or other metallic powder.

When a large amount of oil or other vehicle has been used in thegrinding operation it may be reduced in other ways than by distillation.For example centrifuging or filtration may be utilized. The oil obtainedfrom this operation may be used again.

When nickel carbonate is the source of the raw material it may beadvantageously formed by precipitation from the sulphate of nickel bymeans of soda ash, drying with sodium sulphate present and washing thedried product. In this manner by far the largest proportion of sulphatesare removed Whereas by simple washing of the wet precipitate basicsulphates are liable to be retained to an objectionable degree.

The following represent a series of tests made with different materialsunder different conditions in carrying out the foregoing invention.

Ewample #1.50 parts by weight of nickel carbonate was ground with 300parts by weight of mineral oil in a pebble mill for a period o f 4hours. The ground product on removal from the pebble mill had aconsistency of a thin cream. The ground material in oil was heated to atemperature of 350-360 C. and maintained at this Point for a period ofone hour or until the carbonate had been reduced to a catalyticallyactive material. Upon testing the catalyst in the apparatus describedpreviously in the specification we found that the initial time requiredfor 250 grams of cottonseed oil to absorb 100 c. c. of hydrogen requiredin the presence of .5 of 1%. of the catalytically active materialproduced by the above operation was 19 seconds. The mean time ofabsorption over a period of one hours hydrogenation was 13.3 seconds.The time required for the absorption of the same volume of hydrogen atthe end of one hours hydrogenation was 13 seconds.

.Ewample #2.50 parts by weight of nickel carbonate was ground in apebble mill with 150 parts by weight of water for a period of 4 hours.At the expiration of this time the ground material was of theconsistency of a thin putty and there was no evidence of grittiness whena small portion of the material was rubbed between the fingers. Under amicro-scopewith' a magnification of 1750 diameters the largest of theparticles appeared to be about the size of an ordinary pin head whilethe majority of the particles were smallerthan this. The ini- 604 tialtime required to absorb 100 c. c. of hydrogen using standard quantitiesof cottonseed oil and catalytically active material was 22 seconds. Themean time of absorption for the same volume of hydrogen during one hoursperiod of hydrogenation was 13.1 seconds and the time required to absorb100 c. c. ofhydrogen at the end of one hours period of hydrogenation was14; seconds.

Example #3.5O parts by weight of nickel carbonate was ground in a pebblemill with 100 parts by weight of petrolatum or petroleum jelly for aperiod of 4 hours. The pebble mill was heated during the grinding to atemperature above that of the melting point of the petrolatum. Theproduct was of a putt-y like consistency. The ground nickel carbonate inpetrolatum was then heated for a period of one hour at a temperature of350360 O. and during this operation 63% of the petrolatum distilled offleaving aproduct containing 40% of nickel and of petrolatum. Thecatalyt-ically active product was then tested in the regular manner. Theinitial time required for 250 grams of cottonseed oil to absorb 100 c.c. of hydrogen in the presence of this catalyst was 30 seconds. The meantime required to absorb this volume of hydrogen during a period of onehours hydrogenation was 12.7 seconds. The time required to absorb thesame volume of hydrogen at the end of one hours hydrogenation was 11seconds. In this case the catalyst worked up to its maximum efficiencysomewhat more slowly than in the examples cited previously, requiringbetween 15 and 16 minutes of hydrogenation to work up to its maximumefficiency.

Example iii-In this case 50 parts by weight of nickel carbonate wasground in a pebble mill with 7 5 parts by weight of kerosene and 25parts by weight of petrolatum.

The resultant product was of a putty-like consistency. The groundcarbonate in the oily vehicle was then reduced to acatalytically activestate at a temperature of 350- 360 C. for a period of one hour. Usingthe standard quantities of oil and catalyst the initial time required toabsjorb 100 c. c. of hydrogen was 30 seconds. The mean time during aperiod of one hours hydrogenation to absorb the same volume of hydrogenwas 13.1 seconds. The time required to ab sorb the same volumeofjhydrogen at the eng of one hours hydrogenation was 13 sec on s.

Example #5..In order toillustrate the increase of eificiency of thecatalytically active material prepared from nickel carbonate ground inoil and then reduced and nickel carbonate which was reduced as re-.ceived the following example is cited. Nickel carbonate as purchasedand which was screened to pass a 60 mesh screen was reduced in para-finwax at a temperature of time required for the absorption of 100 c. c. ofhydrogen was 170 seconds. The mean time for the absorption of the samevolume of hydrogen over a period of one hours hydrogena-tion was 70seconds. The time required to absorb this volume of hydrogen at the endof one hours hydrogenation was seconds. In this case the maximumefficiency of the catalytic material was only obtained after fifteenminutes of hydrogenation.

[Fm-(maple #6'.--.& small quantity of the reduced catalytic materialobtained from Example #5 was ground in a pebble mill for a period of 4hours and the efficiency of the ground material then determined. Thepebble mill was heated to a temperature above the melting point of theparaliin during the grinding operation. The initial time required toabsorb 100 c. c. of hydrogen using standard quantities of oil andcatalytically active material was 30 seconds. The mean time during aperiod of one hours hydrogenation toabsorb the same volume of hydrogenwas 19.4 seconds and the time required to absorb the above volume ofhydrogen at the end of one hours hydrogenation was 20 seconds. In thecase of this catalyst it required 10 minutes time of hydrogenation tobring the catalyst up to its maximum efficiency of 14 seconds.

Ermmple #'7.50 parts by weight of nickel fol-mate was ground with 300parts by weight of white mineral oil in a pebble mill for a period of 4hours. At the end of this time the product was of the consistency of athin cream. The particles of ground nickel formate when viewed under amicroscope with a magnification of. 1750 diameters the largest of themwas approximately the size of the head of a pin while the majority ofthe particles were smaller. The ground material was then reduced at atem perature of 250260 C. for a period of one hour. On testing thereduced catalytic material in the apparatus which was described abovethe initial time required for the standard volume of oil with thestandard quantity of catalytic materialwas 15 seconds. The mean time was11.2 seconds. The time required over a period of one hours hydrogenationfor the absorption of c. c. of hydrogen was 11.1 seconds. The timerequired to absorb the same volume of hydrogen at the end of one hourshydrogenation was 14 seconds.

Example #8.-Nickel formate was ground dry to pass 200 mesh bolting clothand was reduced in paraffin at a temperature of 250-260 C. for a periodof one hour. Upon testing the reduced catalytic material in the abovetesting apparatus we found that the initial time for the absorption of100 c. c. of hydrogen was 15 seconds, the mean time required over aperiod of one hours hydrogenation for the absorption of the same volumeof hydrogen was 15.5 seconds. The time required to absorb 100 c c. ofhydrogen at the end of one hours period of hydrogenation was 18 seconds.Standard quantities of oil and catalyzer was used in the above example.

In comparison with the foregoing and indicative of results which may beobtained by grinding nickel alone the following test was made: Nickelflake such as is obtained by the Edison process and which in itself hasbeen recommended as catalytic material was subjected to grinding for aperiod of 7 2 hours in a ball mill. Although the nickel flake is itselfextremely thin and light this great length of grinding was necessary in.

order to secure a catalyzer which had a mean time of absorption over aperiod of one hours hydrogenation of only 65 seconds in comparison withone made from nickel carbonate by grinding the latter in oil and thenreducing, which under like conditions had a mean time of absorption overa period of one hours hydrogenation of 13 seconds.

From the foregoingit will be observed that catalyzers may be rated onthe basis of the time taken to absorb a definite amount of hydrogen gasfor example in the present case 100 c. c., and such rating or numericalexpression may be used to indicate the initial absorptive power or theaverage absorptive power over a given period, say one hour. Both ratingsare used in the consideration of the activity of the catalyzer, namely,its initial speed of absorption and its average speed over 60 minutesduration. The former may be misleading because some catalyzers start offbriskly absorbing the gas and then fall rapidly in power after a fewminutes hydrogenation. Others gain in speed as the hydrogenationprogresses then after a certain point show perhaps uniform absorptionover a considerable subsequent period. The average absorption over onehour is therefore perhaps the best index of the quality of thecatalyzer.

A. rather interesting method of making catalyzer which maybe employed inspecial cases is that of grinding the catalytic raw material, forexample, nickel hydroxid in water. The hydroxid may be freshlyprecipitated and in its moist state placed in a ball mill or edge runnerand ground to the requisite condition of fineness. Then this moist puttymay be projected in small quan tities at a time into a tank of heatedoil soas to expel the moisture quickly. The tank should be capacious inorder to permit of foaming. When the oil contains a sufficient. quantityof the hydroxid or dried product the mixture may be reduced either bytreatment with a reducing gas or by the cracking process aforesai or inany other suitable manner.

lot)

" objectionable.

In the foregoing operations the description has referred mainly togrinding the catalytic material without the presence of any abrasivebody but it should be understood that in all such'cases it is possibleto have present a quantity of abrasive substance such as finely powderedpumice, silex, quartz dust, carborundum and the like. The presence ofsuch an abrasive facilitates the grinding more or less but has thedisadvantage that it increases the wear and tear on the grindingapparatus and frequently in the case of steel grinding vesselsintroduces so large a percentage of iron in the catalyzer that itsactivity is. impaired and the iron in this finely divided state may betaken up by the, oil causing discoloration of the material. Thus whileabrasive may be used it is not necessary and is frequently There is noobjection however to the addition to the finished catalyzer of asufficient amount of bulking material such as silex to enable thecatalyzer to be readily filtered. By protracted grinding of thecatalyzerraw material in the oil to produce the fine suspensions referred toabove the reduced nickel partakes to a considerable extent of the moreor less colloidal condition of the original unreduced ground materialand such colloidal material is, in the hydrogenation process, not easilyfiltered from oils in some cases without the presence of suitablebulking material aforesaid' In the foregoing reference has been made Ito extraction of the catalyzer with a solvent such as benzol, ether, andthe like and by such method or any other suitable extraction method thedry powdered catalytic metal such as nickel which is obtained retains,as stated, for a considerable time its catalytic activity when exposedto the air. It will however oxidize quicklv when heated slightly or whena portion is ignited, this oxidation frequently spreading throughout themass. If moistened with water the catalytic activity is usually impairedin some cases. Thus by the foregoing method a dry powdered catalyzer maybe obtained which may be introduced into any other sealing medium ifdesired or may be packaged in containers which if desired are filledwith an inert gas such as hydrogen or nitrogen.

What we claim is: 1. The process of making a catalyzer concentrate whichcomprises grinding nickel formate in an oil vehicle, continuing thegrinding operation until the potential-catalytie properties are verysubstantially enhanced, and subjecting the ground material to reducingconditions whereby catalyzer is obtained. 7

2. In the process of making a hydrogenating catalyst by reducingcatalytic raw material in a vehicle the steps which comprise firstgrinding the catalytic raw material in 64 in a vehicle the steps whichcomprise first grinding the catalytic raw material in a vehicle which issubstantially liquid at the temperature of the grinding operation,reducing to form the catalytic substance in the vehicle and finallygrinding said catalytic substance while in said vehicle.-

4. In the process of making'a hydrogenating catalyst by reducing a basicpotentially catalytic metallic compound readily reducible sulfur-freecompound of a metal having an atomic weight between 58 and 64 in avehicle the steps which comprise first grinding the catalytic rawmaterial in the vehicle, reducing to form the catalytic substance in thevehicle and finally grinding said catalytic substance while insaidvehicle.

' CARLETON ELLIS.

HARRY M. WEBER.

